Activating intramolecular singlet exciton fission by altering π-bridge flexibility in perylene diimide trimers for organic solar cells

被引：27

作者：

Carlotti, Benedetta ^{[1
,2
]}

Madu, Ifeanyi K. ^{[1
]}

Kim, Hyungjun ^{[1
,3
]}

Cai, Zhengxu ^{[4
]}

Jiang, Hanjie ^{[1
]}

Muthike, Angelar K. ^{[1
]}

Yu, Luping ^{[4
]}

Zimmerman, Paul M. ^{[1
]}

Goodson, Theodore, III ^{[1
]}

机构：

[1] Univ Michigan, Dept Chem, Ann Arbor, MI 48109 USA

[2] Univ Perugia, Dept Chem Biol & Biotechnol, Via Elce Sotto 8, I-06123 Perugia, Italy

[3] Incheon Natl Univ, Dept Chem, Incheon 22012, South Korea

[4] Univ Chicago, James Franck Inst, Dept Chem, 929 East 57th St, Chicago, IL 60637 USA

来源：

CHEMICAL SCIENCE | 2020年 / 11卷 / 33期

基金：

美国国家科学基金会;

关键词：

CHARGE-TRANSFER; SYMMETRY-BREAKING; THIN-FILMS; STATE; GENERATION; SEPARATION; DYNAMICS; MOLECULES; PENTACENE; ANALOG;

D O I：

10.1039/d0sc03271a

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

In this study, two analogous perylene diimide (PDI) trimers, whose structures show rotatable single bond pi-bridge connection (twisted)vs.rigid/fused pi-bridge connection (planar), were synthesized and investigated. We showviatime resolved spectroscopic measurements how the pi-bridge connections in A-pi-D-pi-A-pi-D-pi-A multichromophoric PDI systems strongly affect the triplet yield and triplet formation rate. In the planar compound, with stronger intramolecular charge transfer (ICT) character, triplet formation occursviaconventional intersystem crossing. However, clear evidence of efficient and fast intramolecular singlet exciton fission (iSEF) is observed in the twisted trimer compound with weaker ICT character. Multiexciton triplet generation and separation occur in the twisted (flexible-bridged) PDI trimer, where weak coupling among the units is observed as a result of the degenerate double triplet and quintet states, obtained by quantum chemical calculations. The high triplet yield and fast iSEF observed in the twisted compound are due not only to enthalpic viability but also to the significant entropic gain allowed by its trimeric structure. Our results represent a significant step forward in structure-property understanding, and may direct the design of new efficient iSEF materials.

引用

页码：8757 / 8770

页数：14

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